JPH0452298A - Production of steel sheet with one side plated with electrolytic lead-tin alloy and having iron surface to be excellently phosphated - Google Patents
Production of steel sheet with one side plated with electrolytic lead-tin alloy and having iron surface to be excellently phosphatedInfo
- Publication number
- JPH0452298A JPH0452298A JP16307890A JP16307890A JPH0452298A JP H0452298 A JPH0452298 A JP H0452298A JP 16307890 A JP16307890 A JP 16307890A JP 16307890 A JP16307890 A JP 16307890A JP H0452298 A JPH0452298 A JP H0452298A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- treatment
- plated
- steel sheet
- electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 67
- 239000010959 steel Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 10
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 title claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 35
- 229910052742 iron Inorganic materials 0.000 title abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 60
- 239000000956 alloy Substances 0.000 claims abstract description 60
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 45
- 239000010452 phosphate Substances 0.000 claims abstract description 45
- 229910020220 Pb—Sn Inorganic materials 0.000 claims abstract description 41
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims description 58
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical class OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910018104 Ni-P Inorganic materials 0.000 claims description 3
- 229910018536 Ni—P Inorganic materials 0.000 claims description 3
- 229910017709 Ni Co Inorganic materials 0.000 claims description 2
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 2
- 229910000978 Pb alloy Inorganic materials 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract 1
- 150000008043 acidic salts Chemical class 0.000 abstract 1
- 238000007743 anodising Methods 0.000 abstract 1
- 229960001755 resorcinol Drugs 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 18
- 238000007747 plating Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 238000010422 painting Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 229910000158 manganese(II) phosphate Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052827 phosphophyllite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical class F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、非メッキの鉄面か、リン酸塩処理性と塗装性
能にすぐれた片面電気Ｐｂ−Ｓｎ系合金メッキ鋼板の製
造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing a non-plated iron surface or a single-sided electrical Pb-Sn alloy plated steel sheet with excellent phosphating properties and painting performance. It is.
（従来の技術）
Ｐｂ−Ｓｎ合金電気メッキ鋼板は特開昭５４−８６３３
８号公報で紹介されているが、最近では自動車或いはオ
ートバイ用の燃料容器鋼板として、片面Ｐｂ−Ｓｎ系合
金メッキ鋼板の開発が要望されている。(Prior art) Pb-Sn alloy electroplated steel sheet is disclosed in Japanese Patent Application Laid-Open No. 54-8633.
As introduced in Publication No. 8, there has recently been a demand for the development of a Pb-Sn alloy plated steel sheet on one side as a fuel container steel sheet for automobiles or motorcycles.
すなわち、燃料容器の内面は、ガソリン等の燃料に対し
て、すぐれた耐食性能を有するｐｂ −Ｓｎ系合金のメ
ッキ層であり、燃料容器の外面は、防食と装飾塗装を行
なうことのできる燃料容器用の素材に対する業界の要望
が大きい。That is, the inner surface of the fuel container is plated with a pb-Sn alloy that has excellent corrosion resistance against fuels such as gasoline, and the outer surface of the fuel container is coated with a decorative coating for corrosion protection. There is great demand from the industry for materials for
このＰｂ−Ｓｎ系合金片面メッキ鋼板は、一般にはＰｂ
＋２イオンとＳｎ＋２イオンを含有する水溶液中で、鋼
帯の片面メッキ側に対向して設けられた電極に通電する
陰極電解処理法で製造されている。This Pb-Sn alloy single-sided plated steel sheet is generally made of Pb
It is manufactured using a cathodic electrolytic treatment method in which electricity is applied to an electrode placed opposite the single-sided plated side of the steel strip in an aqueous solution containing +2 ions and Sn+2 ions.
（発明が解決しようとする課題）
しかしながら、非メッキ面には、通常の方法では極く微
量のｐｂおよびＳｎ金属が、如何に電解方法を工夫して
も付着してしまう。(Problems to be Solved by the Invention) However, in the normal method, very small amounts of PB and Sn metals adhere to the non-plated surface no matter how devised the electrolytic method is.
すなわち、非メッキ面に電解液の付着阻止剤を塗布する
ような煩雑な方法を施さない限り、非メッキ面への電解
電流まわり込みを阻止するような方法、例えば電極の幅
を鋼帯幅よりも狭くする方法や、鋼帯の両端にダミーカ
ソードを近接して設ける方法等を講じても、Ｐｂ″″２
．Ｓｎ“２イオン、特にｐｂ”イオンのつき廻り性が良
好なため、極く微量のＰｂ−Ｓｎ合金が付着することを
免れることができない。このように非メッキ面に極く微
量のＰｂ−Ｓｎ合金が付着すると、第１図に示すように
、塗装下地処理のリン酸処理性が著しく阻害される。In other words, unless a complicated method such as applying an electrolyte adhesion inhibitor to the non-plated surface is applied, there is a method to prevent the electrolytic current from flowing to the non-plated surface, such as making the width of the electrode smaller than the width of the steel strip. Even if methods such as narrowing the width of the steel strip or providing dummy cathodes close to both ends of the steel strip,
．． Since the permeability of Sn "2 ions, especially pb" ions is good, it is inevitable that a very small amount of Pb-Sn alloy will adhere. If a very small amount of Pb-Sn alloy adheres to the non-plated surface in this way, as shown in FIG. 1, the phosphoric acid treatment properties of the paint base treatment will be significantly inhibited.
その結果、塗装後の性能、特に腐食環境に長期開−され
た後の経時塗料密着性、或いは塗装後耐食性等が著しく
劣化する。そのため非メッキ面に電解処理を施して付着
したＰｂ−Ｓｎ合金を除去する必要があった。As a result, the performance after painting, especially the adhesion of the paint over time after being exposed to a corrosive environment for a long period of time, or the corrosion resistance after painting, etc. deteriorate significantly. Therefore, it was necessary to perform electrolytic treatment on the non-plated surface to remove the attached Pb-Sn alloy.
しかしながら、この方法によって処理された鋼板はすぐ
れたリン酸塩処理性を有するものの、処理液か有機酸系
水溶液のため、陽極部で有機酸の酸化か起こり、処理液
の劣化速度か大きいという欠点かあった。すなわち、建
浴直後の溶液で処理した鋼板はすぐれたリン酸塩処理性
を有するが、処理量はが増すと有機酸が分解し、電解能
力が低下する。従ってこのような溶液で十分なリン酸塩
処理性を確保することは困難であった。However, although steel sheets treated by this method have excellent phosphatizing properties, the disadvantage is that the treatment liquid is an organic acid-based aqueous solution, so oxidation of the organic acid occurs at the anode, and the rate of deterioration of the treatment liquid is high. There was. That is, a steel plate treated with a solution immediately after bath preparation has excellent phosphate treatment properties, but as the amount of treatment increases, the organic acid decomposes and the electrolytic ability decreases. Therefore, it has been difficult to ensure sufficient phosphate treatment properties with such solutions.
本発明はこのような問題点を解決するものであって、リ
ン酸塩処理性、塗装性能にすぐれた鉄面を有する片面電
気Ｐｂ−Ｓｎ系合金メッキ鋼板の安定的製造法を提供す
ることを目的とするものである。The present invention is intended to solve these problems, and aims to provide a stable manufacturing method for a single-sided electrically plated Pb-Sn alloy plated steel sheet having an iron surface with excellent phosphating properties and coating performance. This is the purpose.
（課題を解決するための手段）
上記目的を達成するために本発明は、ｐｂ”イオンとＳ
ｎ”イオンを主成分とする水溶液中で、鋼帯の片面に対
向して設けられた電極から通電して陰極電解処理を施し
、得られた片面電気ｐｂ −Ｓｎ系合金メッキ鋼板を水
洗後に、５〜２００ｇ／ｇの硝酸、塩酸、ホウフッ化水
素酸の塩の１種又は２種以上を含有する浴に更にレゾル
シン、ヒドロキノンの１種又は２種をＯ，Ｏ１ｇ／ｊ！
〜ＬＯｇ／Ｄを含有するｐＨが１〜４の水溶液中で０．
１〜３０Ａ／ｄｆｆ１２の電流密度で５〜３０秒間の陽
極電解処理を行ない、次いて２価又は３価の金属イオン
を含有するｐＨ３〜８のリン酸塩の混濁液を圧力０，５
〜５ｋｇ ／ ｃ−で１〜１０秒間の吹き付け処理を行
なうこと、或いはＮｉ 、Ｃｏ、Ｎｉ −Ｃｏ合金、
或いはＮｉ −Ｐ、 Ｃｏ −Ｐ、 Ｆｅ −Ｐ合金及
びこれらの金属の２種以上が含有されるＰ合金をメッキ
面に３〜３０■／ゴを被覆する陰極電解処理を施すこと
を要旨とするリン酸塩処理性にすぐれた鉄面を有する片
面電気鉛−錫系合金メッキ鋼板の製造法である。(Means for Solving the Problems) In order to achieve the above object, the present invention provides pb" ions and S
In an aqueous solution containing n'' ions as a main component, the steel strip is subjected to cathodic electrolytic treatment by applying electricity from electrodes placed opposite to each other on one side of the steel strip, and after washing the resulting single-sided electrolytic PB-Sn alloy plated steel sheet with water, In a bath containing 5 to 200 g/g of one or more of salts of nitric acid, hydrochloric acid, and hydrofluoroboric acid, one or two of resorcinol and hydroquinone are added to O, O1 g/j!
~0.0 in an aqueous solution with a pH of 1 to 4 containing LOg/D.
Anodic electrolysis is carried out for 5 to 30 seconds at a current density of 1 to 30 A/dff12, and then a suspension of phosphate with a pH of 3 to 8 containing divalent or trivalent metal ions is heated to a pressure of 0.5 A/dff.
~5kg/c- for 1-10 seconds, or Ni, Co, Ni-Co alloy,
Alternatively, the gist is to perform cathodic electrolytic treatment to coat the plated surface with Ni-P, Co-P, Fe-P alloys, or P alloys containing two or more of these metals in an amount of 3 to 30 cm/g. This is a method for producing a single-sided electrolytic lead-tin alloy plated steel sheet having an iron surface with excellent phosphating properties.
（作 用） 以下、本発明の詳細な説明する。(for production) The present invention will be explained in detail below.
本発明においてメッキ原板は製鋼工程、圧延工程、焼鈍
工程等を経て製造された冷延鋼板を使用し、さらに、表
面処理鋼板の製造工程の脱脂、酸洗等の前処理が施され
て清浄化、活性化処理が行なわれた後、鋼帯片面のみに
Ｐｂ−Ｓｎ系合金メッキ処理が施される。In the present invention, the plated original plate is a cold-rolled steel plate manufactured through a steel manufacturing process, a rolling process, an annealing process, etc., and is further cleaned by being subjected to pre-treatments such as degreasing and pickling in the manufacturing process of surface-treated steel sheets. After the activation treatment, a Pb-Sn alloy plating treatment is performed on only one side of the steel strip.
鋼帯の片面電気Ｐｂ−Ｓｎ系合金メッキは、Ｐｂ＋２イ
オンとＳｎ“２イオンを主成分とする水溶液を電解メッ
キ浴として用い、鋼板の片面のみに対向して設けられた
電極から通電し、鋼帯の片面のみにＰｂ−Ｓｎ系合金被
覆層が施される。Single-sided electrolytic Pb-Sn alloy plating of a steel strip uses an aqueous solution containing Pb+2 ions and Sn"2 ions as the main components as an electrolytic plating bath, and current is applied from an electrode provided facing only one side of the steel sheet. A Pb-Sn alloy coating layer is applied to only one side of the strip.
このＰｂ−Ｓｎ系合金の電解メッキ浴組成、電解メッキ
条件等については、何ら規定するものではなく、例えば
片面電気Ｐｂ−８ｎ系合金メッキにおいて使用される電
極は、Ｐｂ−Ｓｎ系合金を使用した可溶性電極方式、Ｔ
Ｉ板に白金をクラッドとしたような不溶解電極のいずれ
を用いてもよい。There are no regulations regarding the electrolytic plating bath composition, electrolytic plating conditions, etc. for this Pb-Sn alloy. For example, the electrodes used in single-sided electrolytic Pb-8n alloy plating are Soluble electrode method, T
Any insoluble electrode, such as an I-plate clad with platinum, may be used.
また、電解メッキ浴組成にはｐｂとＳｎの合金組成に対
応したｐｂ“２．Ｓｎ＋２イオンを含有する水溶液、例
えば、ホウフッ化物浴、フェノールスルフォン酸浴、さ
く酸系浴等か用いられる。Further, for the electrolytic plating bath composition, an aqueous solution containing pb"2.Sn+2 ions corresponding to the alloy composition of pb and Sn, such as a borofluoride bath, a phenolsulfonic acid bath, a saccharic acid bath, etc., is used.
その−例を以下に示す。An example is shown below.
（ａ） Ｐｂ−１２％Ｓｎ系合金メッキ組織を目的と
したホウフッ化物浴を用いた電解条件の例電解浴組成
Ｐｂ （ＢＦ４ ） ２ ３００ｇ／ｌＨＢ Ｆ
ａ ８０ ｇ ／ Ｄ有機質添加剤
５ｇ／Ｉ
Ｓｎ （ＢＦ４ ） ２ ５０ｇ／ＤＨ３ＢＯ２３０
ｇ／り
電流密度 ３０Ａ／ｄｍ２
電解温度 ５０”Ｃ
（ｂ） ｐ ｂ −Ｂ％Ｓｎ系合金メッキ組織を目的
としたフェノールスルフォン酸系浴を用いた電解条件の
例
電解浴組成 ＰｂＯ５０ｇ／ｌ
ＳｎＯ４，５ｇ／ｌ
フェノール １５０ｇ／ｌ）
スルフォン酸
有機質添加剤 ＬＯｇ／ｌ
電流密度 ５Ａ／ｄａ２
電解温度 ５５℃
このように、必要とするｐｂとＳｎの合金組成に対応し
たＰｂ″″イオンとＳｎ＋２イオンを含有する水溶液に
電解メッキ浴を用い、必要とするメッキ厚さに対応する
電解量で、鋼帯の片面のみにＰｂ−Ｓｎ系合金メッキ処
理をし、次いで水洗する。(a) Example of electrolytic conditions using a borofluoride bath aimed at forming a Pb-12%Sn alloy plating structure Electrolytic bath composition
Pb (BF4) 2 300g/lHB F
a 80 g/D organic additive
5g/I Sn (BF4) 2 50g/DH3BO230
g/current density 30A/dm2 Electrolysis temperature 50"C (b) p b -B%Example of electrolysis conditions using a phenolsulfonic acid bath for the purpose of forming a Sn-based alloy plating structure Electrolytic bath composition PbO50g/l SnO4, 5g/l Phenol 150g/l) Sulfonic acid organic additive LOg/l Current density 5A/da2 Electrolysis temperature 55℃ In this way, it contains Pb'''' ions and Sn+2 ions corresponding to the required alloy composition of Pb and Sn. Using an electrolytic plating bath in an aqueous solution, the steel strip is plated with a Pb-Sn alloy on only one side with an electrolytic amount corresponding to the required plating thickness, and then washed with water.
しかしながらこのようにして製造された片面Ｐｂ−Ｓｎ
系合金メッキ鋼板の非メッキ面・鉄面には、前記したよ
うに微量のＰｂ、Ｓｎ或はＰ、ｂ−Ｓｎ合金を付着し、
リン酸亜鉛を主成分とするリン酸塩結晶被膜を生成させ
るリン酸塩処理性を著しく阻害し、塗装性能を劣化する
。However, the single-sided Pb-Sn produced in this way
As mentioned above, a trace amount of Pb, Sn or P, b-Sn alloy is attached to the non-plated surface/iron surface of the alloy-plated steel sheet,
It significantly inhibits phosphate treatment, which produces a phosphate crystal film containing zinc phosphate as the main component, and deteriorates coating performance.
そのため非メッキ面に付着した微量のｐｂ −Ｓｎ合金
を除去する処理は極めて重要な工程であり、本発明は、
この処理を目的とするものであるが、次の点に留意しな
ければならない。Therefore, the process of removing trace amounts of pb-Sn alloy attached to the non-plated surface is an extremely important process, and the present invention
Although this processing is intended, the following points must be kept in mind.
すなわち、非メッキ面に付着した微量のｐｂ −ｓｎ合
金の除去作業（操作）において、他面のＰｂ−Ｓｎ系合
金メッキ面に溶解、損傷等を起して耐食性を劣化し、外
観を変色させるなどのメッキ外観に劣化を生じさせない
ことが必要である。In other words, during the removal work (operation) of a small amount of Pb-Sn alloy attached to a non-plated surface, the Pb-Sn alloy plated surface on the other side may be dissolved, damaged, etc., resulting in deterioration of corrosion resistance and discoloration of the appearance. It is necessary not to cause any deterioration in the appearance of the plating.
このような観点から種々検討した結果、処理浴として、
硝酸、塩酸、ホウフッ化水素酸の塩の１種又は２種以上
を混合した水溶液に、更に添加剤として０．０１〜１０
ｇ／ｌのレゾルシン、ヒドロキノンの１種或いは２種を
含有するｐＨが１〜４の水溶液中において、非メッキ面
に対向する側にのみ電極を配置して通電する陽極電解処
理を施すと、メッキ面の耐食性等を阻害することなく、
非メッキ面に付着した微量のＰｂ−Ｓｎ系合金付着物を
除去し、更に添加剤の効果により過剰な陽極電解処理に
対し鋼板を保護することが分った。As a result of various studies from this point of view, as a treatment bath,
Add 0.01 to 10% as an additive to an aqueous solution containing one or more salts of nitric acid, hydrochloric acid, and fluoroboric acid.
When an anodic electrolytic treatment is performed in which an electrode is placed only on the side facing the non-plated surface and electricity is applied in an aqueous solution containing one or both of resorcinol and hydroquinone at a pH of 1 to 4, plating occurs. without affecting the corrosion resistance of the surface, etc.
It has been found that trace amounts of Pb-Sn alloy deposits adhering to non-plated surfaces can be removed, and furthermore, the effect of the additive can protect the steel sheet from excessive anodic electrolytic treatment.
一方、非メッキ面に付着した微量のＰｂ−Ｓｎ系合金付
着物は、鋼板表面に均一に存在するのではなく、鋼の粒
界上に塊状に析出している。この塊状付着物を除去する
陽極電解処理では、該付着物が除去されると同時に、非
メッキ面のエツチング或いは鉄面の酸化が軽微ながら行
なわれることになる。すなわちＰｂ−８ｎ系合金付着物
が完全に除去されても、エツチング或いは鉄面の酸化の
影響のためリン酸塩処理性が必ずしも良好ではない。し
かし、浴中に添加したレゾルシンやヒドロキノンは、非
メッキ面の鋼板上に吸着し、エツチング或いは酸化から
鋼板を保護するとともに陽極電解電流をＰｂ−Ｓｎ系合
金付着物に集中させて、Ｐｂ−Ｓｎ系合金付着物の除去
を極めて効率よく行なう役割を果たす。On the other hand, a small amount of Pb-Sn alloy deposits attached to the non-plated surface do not exist uniformly on the surface of the steel sheet, but are precipitated in lumps on the grain boundaries of the steel. In the anodic electrolytic treatment for removing this lumpy deposit, the deposit is removed, and at the same time, the non-plated surface is etched or the iron surface is slightly oxidized. That is, even if the Pb-8n alloy deposits are completely removed, the phosphating property is not necessarily good due to the influence of etching or oxidation of the iron surface. However, resorcinol and hydroquinone added to the bath adsorb onto the non-plated surface of the steel sheet, protecting the steel sheet from etching or oxidation, and concentrating the anodic electrolytic current on the Pb-Sn alloy deposits. It plays a role in removing system alloy deposits extremely efficiently.
また、リン酸塩処理性に劣るＴｉ −添加鋼、或いは
リン酸塩処理能力に劣るスプレー型リン酸塩処理におい
て、レゾルシンやヒドロキノン等の添加効果は等しい。Furthermore, in Ti-added steel which has poor phosphate treatment properties or spray-type phosphate treatment which has poor phosphate treatment ability, the effects of adding resorcinol, hydroquinone, etc. are the same.
さらにまた、処理浴の主成分が無機物であることおよび
有機物添加剤が芳香族のため分解されにくいことから、
長時間の処理においても浴の変色などの変質は生じず、
安定的に処理し得る特性がある。Furthermore, since the main components of the treatment bath are inorganic and the organic additives are aromatic, they are difficult to decompose.
Even during long-term treatment, there is no change in quality such as discoloration of the bath.
It has the property of being able to be processed stably.
以上の効果を得るためには、次のような処理条件を採用
する。In order to obtain the above effects, the following processing conditions are adopted.
すなわち、硝酸、塩酸、ホウフッ化水素酸の塩の１種又
は２種以上からなるｐＨが１〜４の水溶液を使用し、そ
の濃度は５ｇ／Ｄ〜２００ｇ／１１、好ましくは５０ｇ
／Ｄ〜１５０ ｇ／ｌの範囲である。That is, an aqueous solution containing one or more salts of nitric acid, hydrochloric acid, and fluoroboric acid and having a pH of 1 to 4 is used, and its concentration is 5 g/D to 200 g/11, preferably 50 g.
/D to 150 g/l.
濃度か５ｇ／１未満では非メッキ面に付着したＰｂ−Ｓ
ｎ系合金の付着物を除去することが困難であるとともに
、充分な電気型導度か得られない。If the concentration is less than 5g/1, Pb-S adheres to the non-plated surface.
It is difficult to remove deposits of n-based alloys, and sufficient electrical type conductivity cannot be obtained.
またその濃度か２００ｇ／ｌ）を超えると、他のメッキ
面のＰｂ−８ｎ系合金メッキ層を溶解して耐食性を劣化
し、変色による外観性を劣化する。Moreover, if the concentration exceeds 200 g/l), the Pb-8n alloy plating layer on other plated surfaces will be dissolved, the corrosion resistance will deteriorate, and the appearance will deteriorate due to discoloration.
レゾルシン或いはヒドロキノンの１種又は２種からなる
添加剤の濃度は０．０１ｇ／ｉ）〜１０ｇ／ｆｌ。The concentration of the additive consisting of one or both of resorcinol and hydroquinone is 0.01 g/i) to 10 g/fl.
好ましくは０．１ｇ／ｌ〜Ｉｇ／Ｉｌｌである。濃度が
０．０１ ｇ ７１１未満では添加剤が非メッキ面上を
均一に覆うことが困難であり、１０ｇ／（１以上では効
果が飽和する。Preferably it is 0.1 g/l to Ig/Ill. If the concentration is less than 0.01 g/(1), it is difficult for the additive to uniformly cover the non-plated surface, and if it is 10 g/(1 or more), the effect is saturated.
水溶液のｐＨは１〜４、好ましくは１．５〜３である。The pH of the aqueous solution is 1-4, preferably 1.5-3.
ｐＨが１未満では鉄面のエツチングが大きく、良好な化
成処理性が得られないばかりか、メッキ面であるＰｂ−
Ｓｎ系合金メッキ層を溶解、損傷し、耐食性の劣化を促
す。ｐＨが４以上においてはコロイド状に鉛が析出する
ため、これが鋼板上に付着したり、ロールに付着して押
し疵の原因となる。また、この現象を利用して処理液中
の鉛を除去し、処理液の寿命を長くすることも可能であ
る。If the pH is less than 1, the etching of the iron surface will be large and good chemical conversion treatment properties will not be obtained, and the Pb-
Dissolves and damages the Sn-based alloy plating layer and promotes deterioration of corrosion resistance. When the pH is 4 or more, lead is precipitated in colloidal form, and this adheres to the steel plate or rolls, causing indentation scratches. Furthermore, it is also possible to utilize this phenomenon to remove lead from the processing solution and extend the life of the processing solution.
すなわち、処理液のｐＨを水酸化ナトリウム等で４以上
とし、鉛をコロイドとして析出させる。静止によりコロ
イドを沈殿、除去したのち、上澄み液のｐＨを１〜４に
調製することにより処理液を長期にわたって使用するこ
とが可能である。That is, the pH of the treatment liquid is adjusted to 4 or higher using sodium hydroxide or the like, and lead is precipitated as a colloid. After the colloid is precipitated and removed by standing still, the pH of the supernatant solution is adjusted to 1 to 4, thereby making it possible to use the treatment solution for a long period of time.
尚、本発明に使用される硝酸、塩酸、ホウフッ化水素酸
の塩としては、Ｎａ塩、Ｋ塩、アンモニウム塩が使用さ
れる。Note that as the salts of nitric acid, hydrochloric acid, and fluoroboric acid used in the present invention, Na salts, K salts, and ammonium salts are used.
また非メッキ面の陽極電解処理条件は、電流密度：０．
ＩＡ／ｄａ２〜３０Ａ／ｄａ２に規定する。電流密度が
Ｏ，ｌＡ／ｄａ２未満では、非メッキ面に付着したＰｂ
−Ｓｎ系合金付着物の除去に時間かかかりすぎ、メッキ
面のＰｂ−Ｓｎ合金層の損傷を生じる。また、電流密度
か３０Ａ／ｄ厘２を超えると、その除去効果が飽和する
とともに、電極と鋼帯との間にかかる電解電圧が大きく
なり、電力費が増大するばかりでなく、Ｆｅの酸化をも
たらすため好ましくない。また、好ましい電流密度は０
．５〜５Ａ／ｄａ２の範囲である。The conditions for anodic electrolytic treatment of the non-plated surface were as follows: current density: 0.
It is defined as IA/da2 to 30A/da2. When the current density is less than O,lA/da2, Pb attached to the non-plated surface
- It takes too much time to remove the Sn-based alloy deposits, causing damage to the Pb-Sn alloy layer on the plated surface. Furthermore, if the current density exceeds 30 A/d2, the removal effect will be saturated and the electrolytic voltage applied between the electrode and the steel strip will increase, which not only increases power costs but also reduces the oxidation of Fe. undesirable because it causes Also, the preferred current density is 0
．． It is in the range of 5 to 5 A/da2.
また、その電解処理時間は、０．５〜３０秒間である。Moreover, the electrolytic treatment time is 0.5 to 30 seconds.
０．５秒未満では非メッキ面のＰｂ−Ｓｎ系合金付着物
が均一に除去されにくく、また３０秒を超えるとメッキ
面のＰｂ−Ｓｎ系合金メッキ層を溶解、損傷し、耐食性
の劣化及び外観変色等の劣化を生じ易くなる。従って、
処理時間は０．５秒〜３０秒間で好ましくは５〜２０秒
間である。If it is less than 0.5 seconds, it will be difficult to uniformly remove the Pb-Sn alloy deposits on the non-plated surface, and if it exceeds 30 seconds, the Pb-Sn alloy plating layer on the plated surface will be dissolved and damaged, resulting in deterioration of corrosion resistance and Deterioration such as external discoloration is likely to occur. Therefore,
The treatment time is 0.5 seconds to 30 seconds, preferably 5 to 20 seconds.
次に処理浴の温度については特に限定するものではない
か、処理温度は２０〜８０℃が好ましい。処理温度が２
０℃未満では、除去速度が遅く処理時間が長くかかり過
ぎ、又処理温度が８０℃を超えると処理浴にフユーム、
ミストを発生し、作業環境上好ましいものでなく、メッ
キ面のＰｂ−Ｓｎ系合金メッキ層も変色し易い。Next, the temperature of the treatment bath is not particularly limited, and the treatment temperature is preferably 20 to 80°C. Processing temperature is 2
If the temperature is below 0°C, the removal rate will be slow and the processing time will be too long, and if the processing temperature exceeds 80°C, fumes will be present in the processing bath.
It generates mist, which is not favorable in terms of the working environment, and the Pb-Sn alloy plating layer on the plating surface is also prone to discoloration.
以上の如き処理条件、処理方法で非メッキ面のＰｂ−Ｓ
ｎ系合金の付着物を除去した後水洗する。Pb-S on the non-plated surface under the above treatment conditions and treatment method.
After removing the deposits of the n-based alloy, it is washed with water.
しかし、非メッキ面が鉄面状態では、リン酸塩結晶の生
成を阻害するＰｂ−Ｓｎ系合金付石物は除去されている
か、リン酸塩結晶の生成に必要なマイクロセル形成に必
要な酸化膜が存在せず、そのためにリン酸塩結晶が粗大
化し、ひいては塗装後耐食性が劣化する場合がある。し
たかって、本発明は非メッキ面のリン酸塩処理性と塗装
後件能を確保するために、非メッキ面に付着したｐｂＳ
ｎ系合金付着物を除去し、次いで水洗或いはブラッシン
グした後、リン酸塩結晶核生成促進処理を施す。However, if the non-plated surface is an iron surface, the Pb-Sn alloy stones that inhibit the formation of phosphate crystals have been removed, or the oxidation necessary for the formation of microcells necessary for the formation of phosphate crystals has been removed. There is no film, which causes the phosphate crystals to become coarser, which may lead to a deterioration in corrosion resistance after painting. Therefore, the present invention aims to remove pbS adhered to the non-plated surface in order to ensure the phosphatizing properties of the non-plated surface and the performance after painting.
After removing n-based alloy deposits and then washing with water or brushing, a phosphate crystal nucleation promotion treatment is performed.
一般に、リン酸塩結晶の鋼板表面に対する生成は、以下
のように考えられる。Generally, the formation of phosphate crystals on the surface of a steel sheet is considered as follows.
すなわちリン酸塩処理液の主成分は酸性リン酸亜鉛（Ｚ
ｎ（Ｈ４Ｆ ０４ ） ２ ）であり、溶液中では（１
）式のような平衡が成立する。In other words, the main component of the phosphate treatment solution is acidic zinc phosphate (Z
n(H4F 04 ) 2 ), and (1
) is established.
３ Ｚ ｎ ”＋ ２ Ｈ２Ｐ ０４２− ：Ｚｎ３
（ＰＯ４）２ ＋４Ｈ” −−（１）この溶液中に
鋼板が浸漬されると、鋼板表面で次の溶解反応が起こる
。3 Z n ”+ 2 H2P 042- :Zn3
(PO4)2 +4H'' --(1) When a steel plate is immersed in this solution, the following dissolution reaction occurs on the surface of the steel plate.
Ｆ ｅ＋ ２ Ｈ” →Ｆ ｅ ”十Ｈ２−−（２）こ
の溶解をミクロ的にみた場合、局部アットでＦｅ２＋の
生成、局部カソードでＨ２の発生のカップル反応（ミク
ロセル）を形成している。局部カソードではＨ“イオン
か消費されるために、（１）式の平衡が破れて反応か右
へ進み、ｐ）Ｉの上昇とともに難溶性のＺ ｎ ３
（Ｐ ０４ ） ２の結晶（ホバイト、Ｚｎ、（ＰＯ４
）２ ’４Ｈ２０）か沈殿析出する。たたし、被膜の主
成分はホパイトであるが、界面に存在するＦｅ”の一部
かＺｎと置換したＺｎ３ Ｆｅ（ＰＯ４）２ ”４Ｈ２
０（ホスホフィライト）も少量形成される。Fe+ 2 H" → Fe "10H2-- (2) When this dissolution is viewed microscopically, a coupled reaction (microcell) is formed in which Fe2+ is generated at the local at and H2 is generated at the local cathode. Since H" ions are consumed at the local cathode, the equilibrium of equation (1) is broken and the reaction proceeds to the right, and as p)I increases, poorly soluble Z n 3
(P 04 ) 2 crystals (hovite, Zn, (PO4
)2'4H20) or precipitate. However, the main component of the film is hopite, but some of the Fe'' present at the interface or Zn3 Fe(PO4)2''4H2 substituted with Zn.
0 (phosphophyllite) is also formed in small amounts.
以上のように、鋼板に対するリン酸塩結晶の析出部は鉄
の局部カソード部であり、時間とともに順次カソード、
アノードの位置を変えなから全面に被膜を形成する。し
たがって、リン酸塩結晶の析出反応は、鋼表面の性質に
依存する電気化学的反応であり、鋼板表面に多数のミク
ロセルを形成するものでは、緻密なリン酸塩被膜か形成
される。As mentioned above, the precipitated part of phosphate crystals on the steel plate is the local cathode part of iron, and over time, the cathode,
A film is formed on the entire surface without changing the position of the anode. Therefore, the precipitation reaction of phosphate crystals is an electrochemical reaction that depends on the properties of the steel surface, and if a large number of microcells are formed on the surface of the steel sheet, a dense phosphate film is formed.
このミクロセルの形成に対して、鋼板表面の不可視的な
酸化膜の影響が大きく、酸化膜の厚さによって、その結
晶核の生成状況および生成する結晶核の大きさが著しく
影響される。そのため、酸化膜が除去された鋼板表面は
、均一清浄化された表面であるためミクロセル形成のた
めの活性源が消失し、結晶核の生成数が減少し、粗大な
リン酸塩結晶しか生成されなくなる傾向にある。The invisible oxide film on the surface of the steel sheet has a large influence on the formation of microcells, and the thickness of the oxide film significantly influences the formation of crystal nuclei and the size of the crystal nuclei produced. Therefore, since the surface of the steel sheet from which the oxide film has been removed is a uniformly cleaned surface, the active source for microcell formation disappears, the number of crystal nuclei generated decreases, and only coarse phosphate crystals are generated. It tends to disappear.
この傾向は、片面電気Ｐｂ−８ｎ系合金メッキ鋼板の非
メッキ面についても同様で、均一で緻密なリン酸塩結晶
核を生成させ、ひいては塗装後の性能、特に経時後の密
着性、耐食性等を向上させるためには、その鉄面に酸化
膜に代わる多数のミクロセルの形成を可能にする対策を
講じる必要がある。This tendency is the same for the non-plated surface of single-sided electric Pb-8n alloy plated steel sheets, which generates uniform and dense phosphate crystal nuclei, which in turn improves the performance after painting, especially the adhesion and corrosion resistance after aging. In order to improve this, it is necessary to take measures to enable the formation of a large number of microcells on the iron surface in place of the oxide film.
この対策として、種々検討の結果、鋼板ストリップの非
メッキ面に、２価または３価の金属のイオンを含むリン
酸塩の懸濁液の吹き付け処理、特に好ましくはリン酸亜
鉛の懸濁液の吹き付け処理を行なって、酸化膜に代わる
多数のミクロセルを形成する活性源を付与することが効
果的であることがわかった。As a countermeasure against this, as a result of various studies, we have found that the non-plated surface of the steel sheet strip is sprayed with a suspension of phosphate containing divalent or trivalent metal ions, and particularly preferably with a suspension of zinc phosphate. It has been found that it is effective to apply a spraying treatment to provide an active source that forms a large number of microcells in place of the oxide film.
すなわち金属イオンを含むリン酸塩の懸濁液の吹き付け
により、非メッキ面に微細な機械的加工効果が生じ、こ
れによる表面の不均一エネルギー部位の発生、および吹
き付け処理された極く微細で微少量の反応生成物の生成
により、これらが次に行なわれるリン酸塩結晶核発生の
源となり、リン酸塩結晶核の生成を著しく促進して均一
緻密なリン酸塩結晶を生成させるとともに、塗装後の性
能を著しく向上させる。That is, the spraying of a suspension of phosphate containing metal ions produces a fine mechanical processing effect on the non-plated surface, which leads to the generation of non-uniform energy sites on the surface and to the sprayed extremely fine and fine particles. Due to the formation of a small amount of reaction products, these become the source of the subsequent phosphate crystal nucleation, which significantly accelerates the phosphate crystal nucleation to produce uniform and dense phosphate crystals, as well as coating. Significantly improves subsequent performance.
この金属イオンを含むリン酸塩の懸濁液の吹き付け処理
においては、得られる効果の程度、生産性、操業上の問
題から、Ｚｎ３ （ＰＯ４）２ ・５Ｈ２０等のｌＯ
〜１００ ｇ／ｌ （好ましくは２０〜５０ｇ／ｌ）
をコロイド状に懸濁させ、リン酸でｐＨ３〜８（好まし
くはｐＨ４〜７）にｐＨ調整した懸濁液を圧力０．５〜
５ｋｇ／ｃシ（好ましくは１．５〜３．５ｋｇ ／ｃｄ
）の圧力で、好ましくは常温〜６０℃で１〜ｌＯ秒間
（好ましくは２〜５秒間）吹き付ける。懸濁液としては
この他にＣｕ３ （ＰＯ４）２ 。In the spraying treatment of a suspension of phosphate containing metal ions, due to the degree of effect obtained, productivity, and operational problems, it is necessary to use lO such as Zn3 (PO4)2 .
~100 g/l (preferably 20-50 g/l)
was suspended in colloidal form, and the pH was adjusted to pH 3 to 8 (preferably pH 4 to 7) with phosphoric acid.
5kg/cd (preferably 1.5-3.5kg/cd
), preferably at room temperature to 60° C., for 1 to 10 seconds (preferably 2 to 5 seconds). In addition to this, Cu3 (PO4)2 is used as a suspension.
Ｍｇｓ （ＰＯ４）２．Ｍｎ３ （ＰＯ４）２ 、
Ｆｅ（ＰＯ４）等のリン酸塩を水に懸濁したものが使用
される。また、鋼板表面にＦｅよりもリン酸塩水溶液中
で溶解しにくいＮｉ 、Ｃｏ、Ｎｉ −Ｃ。Mgs (PO4)2. Mn3(PO4)2,
A phosphate such as Fe(PO4) suspended in water is used. In addition, Ni, Co, and Ni-C are more difficult to dissolve in a phosphate aqueous solution than Fe on the steel plate surface.
合金、もしくはＮｉ −Ｐ、 Ｃｏ −Ｐ、 Ｆｅ
−Ｐまたはこれらの金属の２種以上が含有されるＰ合金
を電析させ、Ｆｅの局部溶解反応を促進することによっ
ても酸化膜に代わる多数のミクロセルを形成する活性源
になりうる。Alloy or Ni-P, Co-P, Fe
-P or a P alloy containing two or more of these metals can be electrodeposited to promote the local dissolution reaction of Fe, which can also serve as an active source for forming a large number of microcells in place of an oxide film.
これらの金属または合金を鋼板表面に付与するには、前
記したイオンを含有する水溶液中で、鋼帯の非メッキ面
のみに陰極電解処理を行う。しかしながら、その電析に
よる析出形態は不連続に多数の析出核が存在することが
必要であり、付着量としては３〜３０ａ＋ｇ／ｒＴｆで
ある。付着量が３ ｍｇ ／ ｒｒ？未満ではこれらの
電着物かカソードとなり、鋼板面がアノードとなる反応
促進効果が少なく、リン酸塩結晶核の均一緻密な生成に
対する効果が不充分である。また、付＠量が３０■／ゴ
を超えると電着物が連続的に析出するため、鋼板面のア
ノード溶解反応が起こりにくくなり、マイクロセル生成
効果か減じられ、均一緻密なリン酸塩結晶の生成が阻害
される。したかつて、これらの付着量は３−３１１ａｇ
／ ｒｒｒ、好ましくは１０〜１５ｍｇ／ ｒｄの範囲
である。In order to apply these metals or alloys to the surface of the steel sheet, only the non-plated surface of the steel strip is subjected to cathodic electrolysis treatment in an aqueous solution containing the above-mentioned ions. However, the form of the electrodeposition requires the presence of a large number of discontinuous precipitation nuclei, and the amount of deposition is 3 to 30a+g/rTf. The amount of adhesion is 3 mg/rr? If it is less than this, these electrodeposits become cathodes, and the steel sheet surface becomes an anode.The effect of promoting the reaction is small, and the effect on the uniform and dense formation of phosphate crystal nuclei is insufficient. In addition, if the amount exceeds 30 μ/g, electrodeposit will continue to precipitate, making it difficult for the anode dissolution reaction to occur on the steel sheet surface, reducing the microcell generation effect, and creating uniform and dense phosphate crystals. production is inhibited. Previously, the amount of these deposits was 3-311ag
/ rrr, preferably in the range of 10-15 mg/rd.
以上のように、本発明は片面電気Ｐｂ−Ｓｎ系合金メッ
キ鋼板の製造において、非メッキ面に付着されるリン酸
塩処理性、塗装性能に悪影響を及ぼす微量のＰｂ−Ｓｎ
系合金の付着物をメッキ面の性能を劣化させることなく
除去し、さらにリン酸塩結晶の生成を促進することによ
って、これらの複合効果により極めてリン酸塩処理性と
塗装性能にすぐれた片面電気Ｐｂ−Ｓｎ系合金メッキ鋼
板が得られる。As described above, in the production of single-sided electrically plated Pb-Sn alloy steel sheets, trace amounts of Pb-Sn deposited on the non-plated surface, which have an adverse effect on phosphate treatment properties and coating performance, can be applied.
By removing deposits from alloys without deteriorating the performance of the plated surface and promoting the formation of phosphate crystals, the combined effect of these two methods results in a single-sided electrical coating with excellent phosphatability and coating performance. A Pb-Sn alloy plated steel sheet is obtained.
なお、本発明において、Ｐｂ−Ｓｎ系合金メッキの合金
組成は特に規定されるものではなく、ｐｂを主成分にＳ
ｎが１〜５０％、或いはさらにＳｂ、Ｎｉ 、Ｃｏ等の
合金化元素を少量添加したもの等に適用される。In addition, in the present invention, the alloy composition of the Pb-Sn alloy plating is not particularly specified, and Pb is the main component and S
It is applied to those in which n is 1 to 50%, or to which a small amount of alloying elements such as Sb, Ni, and Co are added.
（実 施 例）
冷延鋼帯を４％オルソケイ酸ソーダー水溶液中で脱脂、
１５％ Ｈ２Ｓ Ｏ４水溶液による陰極電解酸洗による
表面清浄化処理、活性化処理後に所定の合金組成、付着
量を目標とした片面Ｐｂ−Ｓｎ系合金メッキを行ない、
メッキ後水洗して、第１表に示すように、本発明の方法
による非メッキ面の微量Ｐｂ−Ｓｎ系合金付着物の陽極
電解処理による除去及び機械的研磨或いは研削処理を行
なって、性能評価試験を行なった。(Example) A cold rolled steel strip was degreased in a 4% sodium orthosilicate aqueous solution.
After surface cleaning treatment and activation treatment by cathodic electrolytic pickling with a 15% H2S O4 aqueous solution, single-sided Pb-Sn alloy plating is performed with the target alloy composition and deposition amount,
After plating, the plate was washed with water, and as shown in Table 1, trace amounts of Pb-Sn alloy deposits on the non-plated surface were removed by anodic electrolytic treatment and mechanical polishing or grinding was performed using the method of the present invention, and the performance was evaluated. I conducted a test.
また、非メッキ面の微量Ｐｂ−Ｓｎ系合金付着物の陽極
電解処理液の劣化の影響を調査するため、所定の電流密
度で２時間の予備電解を行なった浴でも上記と同様の処
理を施し、性能評価試験を行なった。その結果は表に示
すように予備通電処理の有無にかかわらず、目的とする
性能向上効果が極めて大きかった。In addition, in order to investigate the influence of the deterioration of the anodic electrolyte treatment solution due to trace amounts of Pb-Sn alloy deposits on the non-plated surface, the same treatment as above was applied to the bath in which preliminary electrolysis was performed for 2 hours at the specified current density. , a performance evaluation test was conducted. As shown in the table, the intended performance improvement effect was extremely large regardless of the presence or absence of pre-energization treatment.
尚、本発明の片面電気Ｐｂ−Ｓｎ系合金メッキ鋼帯の製
造は、電解処理浴中で鋼帯の板幅より両端から各々２５
關ずつ狭い目標合金組成と同一組成の可溶性電極を鋼帯
の片面に対向して設けるとともに、鋼帯にほぼ平行に、
両端から約８關ずつ離れた位置にダミーカソードを設置
し、極力非メッキ面に電解電流が裏回りするのを防止し
て片面メッキを施した。The single-sided electrically plated Pb-Sn alloy plated steel strip of the present invention is produced in an electrolytic treatment bath with a width of 25 mm from both ends of the steel strip.
A soluble electrode having the same composition as the target alloy composition is provided on one side of the steel strip, and is placed almost parallel to the steel strip.
Dummy cathodes were installed at positions approximately 8 degrees apart from both ends, and single-sided plating was performed by preventing the electrolytic current from going around to the non-plated surface as much as possible.
次に、本発明の方法で製造した片面Ｐｂ−Ｓｎ系合金メ
ッキ鋼板の性能評価については、以下に示す試験方法及
び評価基準によった。Next, the performance of the single-sided Pb-Sn alloy plated steel sheet manufactured by the method of the present invention was evaluated using the test method and evaluation criteria shown below.
評価試験方法及び評価基準
１、非メッキ面の評価試験方法及び評価基準（１）
リン酸塩処理性
浸漬タイプ或いはスプレータイプのリン酸塩処理浴を用
いて、リン酸塩処理後の外観及び走査型電顕（１５００
倍）でリン酸結晶の生成状況を観察して以下の評価基準
で判断した（第１図参照）。Evaluation test method and evaluation criteria 1, evaluation test method and evaluation criteria for non-plated surface (1)
Phosphate Treatment Using an immersion type or spray type phosphate treatment bath, the appearance after phosphate treatment and scanning electron microscopy (1500
The state of formation of phosphoric acid crystals was observed at 100% magnification) and judged based on the following evaluation criteria (see Figure 1).
◎・・・・・・外観が均一で、均一緻密なリン酸塩結晶
生成。◎・・・・・・Uniform appearance and formation of uniformly dense phosphate crystals.
Ｏ・・・・・・外観は均一であるが、リン酸塩結晶やや
粗大。O: The appearance is uniform, but the phosphate crystals are somewhat coarse.
△・・・・・・外観及び走査型電顕によるミクロ観察で
も、リン酸塩結晶の生成していない個所（スケ部分）が
部分的に生成。△・・・Even in appearance and microscopic observation using a scanning electron microscope, phosphate crystals were partially formed in areas where they were not formed (spot areas).
Ｘ・・・・・・外観上明らかにリン酸塩結晶の生成され
ていないスケ部分が認められる。X: There are clearly visible areas where phosphate crystals are not formed.
（２）塗装後の密着性
カチオン電着塗装２０μを施し、中塗り３５μ、上塗り
３０μを各々スプレー塗装して、８５μの３コート塗装
を施した。該試験材に対して、５０℃の蒸溜水中に各々
２４０時間、４８０時間浸漬後直ちに乾燥して２■ｉＸ
２ｍｍの大きさの基盤目を１００マス作成、セロテープ
（登録商標）剥離を行なってその密着性を評価した。(2) Adhesion after painting A cationic electrodeposition coating of 20μ was applied, an intermediate coat of 35μ and a top coat of 30μ were each spray-painted to give a three-coat coating of 85μ. The test materials were immersed in distilled water at 50°C for 240 hours and 480 hours, respectively, and then dried immediately to give 2iX.
100 base grids of 2 mm in size were created and peeled off using Sellotape (registered trademark) to evaluate the adhesion.
◎・・・・・・塗膜の剥離部分が殆んどなく、密着性極
めて良好。◎・・・・・・There are almost no peeled parts of the coating film, and the adhesion is extremely good.
Ｏ・・・・・・塗膜の剥離は明瞭に認められるが、剥離
面積は約５％以下で少なく、塗膜密着性可成り良好。O: Peeling of the paint film is clearly observed, but the peeled area is small at about 5% or less, and the paint film adhesion is quite good.
Δ・・・・・・塗膜の剥離面積５〜２０％で、塗膜密着
性可成り劣る。Δ: The peeled area of the paint film is 5 to 20%, and the adhesion of the paint film is quite poor.
×・・・・・・塗膜の剥離面積が２０％以上で、塗膜密
着性著しく劣る。×: The peeled area of the paint film is 20% or more, and the paint film adhesion is significantly poor.
（３）塗装後耐食性
カチオン電着塗装を２０μ厚さを施し、地鉄に達するス
クラッチ疵を入れて、塗膜欠陥部を対象とした耐食性能
を塩水噴霧試験により評価した。尚、評価は、塩水噴霧
試験３０日間（７２０時間）後のスクラッチ部からのフ
クレ幅及び他の平面部のブリスターの発生状況を加味し
て、以下の基準で評価した。(3) Corrosion resistance after painting A cationic electrodeposition coating was applied to a thickness of 20 μm, scratches reaching the base metal were made, and the corrosion resistance of the defective parts of the coating film was evaluated by a salt spray test. The evaluation was based on the following criteria, taking into consideration the width of blisters from the scratched area and the occurrence of blisters on other flat areas after 30 days (720 hours) of the salt spray test.
◎・・・・・・スクラッチ部の片側の最大フクレ幅か１
．５＋ｌｌ１１以下で、かつ平面部のブリスター発生数
が５個未満。◎・・・・・・Maximum blistering width on one side of the scratch part or 1
．． 5+ll11 or less, and the number of blisters on the flat surface is less than 5.
Ｏ・・・・・・スクラッチ部の片側の最大フクレ幅か３
ｉｓ以下で、かつ平面部のブリスター発生数が１０個未
満。O...Maximum blistering width on one side of the scratch part 3
is or less, and the number of blisters on the flat surface is less than 10.
△・・・・・・スクラッチ部の片側の最大フクレ幅か３
關以下、或いは平面部のブリスターの発生数が２０個未
満。△・・・・・・Maximum blistering width on one side of the scratch part 3
Less than 20 blisters occur below the lid or on the flat surface.
×・・・・・スクラッチ部の片側の最大フクレ幅か３關
以上、或いは平面部のブリスター発生数が２０個以上。×: The maximum blister width on one side of the scratch area is 3 or more, or the number of blisters on the flat area is 20 or more.
２、メッキ面の性能評価試験法及び性能（１）表面外観
Ｐｂ−８ｎ系合金メッキ面を肉眼観察して、その外観評
価を以下の評価基準で評価した。2. Performance evaluation test method and performance of plated surface (1) Surface appearance The Pb-8n alloy plated surface was observed with the naked eye, and its appearance was evaluated using the following evaluation criteria.
◎・・・・・・表面外観の変色なく、均一外観。◎・・・・・・Uniform appearance with no discoloration on the surface.
Ｏ・・・・・・表面変色は若干生じるが、均一外観。O: Slight surface discoloration occurs, but uniform appearance.
△・・・・・・表面変色が若干生じ、部分的に少しむら
発生。△・・・Slight discoloration occurred on the surface, and slight unevenness occurred in some areas.
Ｘ・・・・′・・表面変色著しく、外観は不均一（２）
耐食性
塩水噴霧試験７２時間後の赤錆発生状況を、１０×１０
＊ｎの大きさの３００個のマス目を用い、赤錆が発生し
たマス目を百分率で表示して、以下の評価基準によった
。X...'... Significant surface discoloration, uneven appearance (2)
The occurrence of red rust after 72 hours of the corrosion resistance salt spray test was
*300 squares of size n were used, and the squares in which red rust occurred were expressed as a percentage, based on the following evaluation criteria.
◎・・・・・・赤錆発生率１０％未満。◎・・・・・・Red rust occurrence rate is less than 10%.
Ｏ・・・・・・ 〃２０％未満。O... Less than 20%.
Δ・・・・・・ 〃４０％未満。Δ・・・・・・〃Less than 40%.
×・・・・・・ 〃４０％以上。×・・・・・・〃40% or more.
第１表の結果から、本発明法によって処理した非メッキ
面・鉄面の性能は比較例との対比からも明らかのように
何れも極めてすぐれていることがわかる。From the results in Table 1, it can be seen that the performance of the non-plated surfaces and iron surfaces treated by the method of the present invention are both extremely excellent, as is clear from the comparison with the comparative example.
（発明の効果）
以上のように、本発明法によれば、非メッキ面に付着し
、リン酸塩処理性、塗装性能に悪影響を及ぼす微量のＰ
ｂ−Ｓｎ系合金付着物を、メッキ面の性能を劣化させる
ことなく除去することかできると共にリン酸塩結晶の生
成を促進させ、これらの複合効果でリン酸塩処理性、塗
装密着性は勿論のこと、塗装後の耐食性にもすぐれた片
面Ｐｂ−Ｓｎ系合金メッキ鋼板を得ることができて、そ
の利用価値を増大している。(Effects of the Invention) As described above, according to the method of the present invention, a trace amount of P adheres to the non-plated surface and has a negative effect on phosphate treatment properties and coating performance.
b-Sn alloy deposits can be removed without deteriorating the performance of the plated surface, and it also promotes the formation of phosphate crystals, and the combined effect of these improves phosphate treatment properties and paint adhesion. As a result, it is possible to obtain a single-sided Pb-Sn alloy plated steel sheet that has excellent corrosion resistance after painting, increasing its utility value.
第１図は片面電気Ｐｂ−Ｓｎ系合金メッキ鋼板（Ｓｎ
８％の例）の非メッキ面の微量Ｐｂ−Ｓｎ合金付着量と
リン酸塩処理性の関係を示す図である。
復代理人 弁理士 田村弘明Figure 1 shows a single-sided electric Pb-Sn alloy plated steel sheet (Sn
8% example) is a diagram showing the relationship between the amount of a trace amount of Pb-Sn alloy deposited on the non-plated surface and the phosphate treatment property. Sub-agent Patent Attorney Hiroaki Tamura
Claims (2)
分とする水溶液中で、鋼帯の片面に対向して設けられた
電極から通電して陰極電解処理を施し、得られた片面電
気Ｐｂ−Ｓｎ系合金メッキ鋼板を水洗後に、５〜２００
ｇ／ｌの硝酸、塩酸、ホウフッ化水素酸の塩の１種又は
２種以上を含有する浴に、更にレゾルシン、ヒドロキノ
ンの１種又は２種を０．０１ｇ／ｌ〜１０ｇ／ｌを含有
させたｐＨ１〜４の水溶液中で０．１〜３０Ａ／ｄｍ＾
２の電流密度で０．５〜３０秒間の陽極電解処理を行い
、次いで２価又は３価の金属イオンを含有するｐＨ３〜
８のリン酸塩の混濁液を圧力０．５〜５ｋｇ／ｃｍ＾２
で１〜１０秒間の吹き付け処理を行うことを特徴とする
リン酸塩処理性にすぐれた非メッキ面を有する片面電気
鉛・錫系合金メッキ鋼の製造法。(1) In an aqueous solution containing Pb^+^2 ions and Sn^+^2 ions as main components, electricity was applied through an electrode placed opposite to one side of the steel strip to perform cathodic electrolytic treatment. 5 to 200 after washing one side electric Pb-Sn alloy plated steel plate with water.
g/l of one or more salts of nitric acid, hydrochloric acid, and fluoroboric acid, and further containing one or more of resorcinol and hydroquinone in an amount of 0.01 g/l to 10 g/l. 0.1 to 30 A/dm^ in an aqueous solution with a pH of 1 to 4
Anodic electrolysis treatment is carried out for 0.5 to 30 seconds at a current density of 2, followed by an anodic electrolytic treatment of pH 3 to 3 containing divalent or trivalent metal ions.
A turbid solution of phosphate of No. 8 was heated to a pressure of 0.5 to 5 kg/cm^2.
A method for producing single-sided electrolytic lead-tin alloy plated steel having a non-plated surface with excellent phosphating properties, characterized by carrying out a spraying treatment for 1 to 10 seconds.
分とする水溶液中で、鋼帯の片面に対向して設けられた
電極から通電して陰極電解処理を施し、得られた片面電
気Ｐｂ−Ｓｎ系合金メッキ鋼板を水洗後に、５〜２００
ｇ／ｌの硝酸、塩酸、ホウフッ化水素酸の塩の１種又は
２種以上を含有する浴に更にレゾルシン、ヒドロキノン
の１種又は２種を０．０１ｇ／ｌ〜１０ｇ／ｌを含有す
るｐＨが１〜４の水溶液中で０．１〜３０Ａ／ｄｍ＾２
の電流密度で０．５〜３０秒間の陽極電解処理を行い、
次いでＮｉ、Ｃｏ、Ｎｉ−Ｃｏ合金、或いはＮｉ−Ｐ、
Ｃｏ−Ｐ、Ｆｅ−Ｐ合金及びこれらの金属の２種以上を
含有するＰ合金を非メッキ面に３〜３０ｍｇ／ｍ＾２を
被覆する陰極電解処理を行うことを特徴とするリン酸塩
処理性にすぐれた非メッキ面を有する片面電気鉛・錫系
合金メッキ鋼板の製造法。(2) In an aqueous solution containing Pb^+^2 ions and Sn^+^2 ions as the main components, electricity was applied through an electrode placed opposite to one side of the steel strip to perform cathodic electrolytic treatment. 5 to 200 after washing one side electric Pb-Sn alloy plated steel plate with water.
g/l of one or more salts of nitric acid, hydrochloric acid, or fluoroboric acid, and one or more of resorcinol and hydroquinone at a pH of 0.01 g/l to 10 g/l. 0.1 to 30 A/dm^2 in an aqueous solution of 1 to 4
Perform anodic electrolysis treatment for 0.5 to 30 seconds at a current density of
Next, Ni, Co, Ni-Co alloy, or Ni-P,
Phosphate treatment characterized by performing cathodic electrolytic treatment to coat a non-plated surface with Co-P, Fe-P alloy, or P alloy containing two or more of these metals at a concentration of 3 to 30 mg/m^2 A method for producing a single-sided electrolytic lead/tin alloy plated steel sheet that has a non-plated surface with excellent properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16307890A JPH0452298A (en) | 1990-06-21 | 1990-06-21 | Production of steel sheet with one side plated with electrolytic lead-tin alloy and having iron surface to be excellently phosphated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16307890A JPH0452298A (en) | 1990-06-21 | 1990-06-21 | Production of steel sheet with one side plated with electrolytic lead-tin alloy and having iron surface to be excellently phosphated |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0452298A true JPH0452298A (en) | 1992-02-20 |
Family
ID=15766768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16307890A Pending JPH0452298A (en) | 1990-06-21 | 1990-06-21 | Production of steel sheet with one side plated with electrolytic lead-tin alloy and having iron surface to be excellently phosphated |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0452298A (en) |
-
1990
- 1990-06-21 JP JP16307890A patent/JPH0452298A/en active Pending
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